Discharge printing organic derivatives of cellulose



.dyestufl having direct amnity therefor.

Patented Apr. 13, 1943 nrsonsncr: ramrmc OBGANIODERIVA- TIVES or CELLULOSE Henry Charles Olpin and William Cy l Mc- Knight, Spondon, near Derby, England, assignors to Celanese Corporation of America, a

corporation of Delaware No Drawing. Application September 4, 1940,

In Great Britain October Serial No. 355,310. 20, 1939 12 Claims. (01. 8-64),

This invention relates to the production of pattern effects on textile materials of organic deriva-- tives of cellulose, i. e. of cellulose esters or others. It is especially concerned with the production of such pattern efiects on pale coloured grounds.

The range of dischargeable dyestuil's for pale shades, especially pale blue shades, on cellulose ester or ether materials is not entirely satisfactory owing to the difficulty of finding a really satisfactory colour meeting the various requirements of brightness of shade, fastness to light, dischargeability without hypersensitiveness in pale shades to traces of discharging agent which may have accidentally come in contact with portions of the material other than those printed with the discharge composition, and resistance to steaming and general after processing, including the mild oxidation treatment which is commonly employed when using vat colours as illuminants. These requirements are not so difiicult to meet in medium 7 to full shades since any slight change in the pale blue shades, with anthraquinone derivatives having direct afiinity therefor, for example aminoanthraquin ones, including N -substituted aminoanthraquinones. Since these anthraquinone derivatives meet the various requirements outlined above the pattern effects obtained are of great value.

According to the present, invention, therefore, cellulose acetate or other cellulose ester or ether materials exhibiting pattern effects on pale coloured grounds are obtained by locally applying a sulphoxylate discharging agent to cellulose acetate or other cellulose ester or ether materials coloured in pale shades with an anthroquinone As discharging agent there can be used, for example, zinc formaldehyde v sulphoxylate or sodium formaldehyde sulphoxylate.

The possibility of obtaining in this way pattern effects on materials dyed with anthraquinone dyestuffs oi the above type is most surprising, since these dyestuffs have always been regarded as nondischargeable. However, in pale shades, for example, theshades obtainable using up to 0.05% or even 0.1% of dyestuff, based on the weight ofthe goods, these anthraquinone derivatives have been found to be sufllciently dischargeable with, for example, the normal alkaline discharge pastes to enable the discharged portions to be illuminated with vat or other'colours without the residual colour of the reduced anthraquinone dyestufl appreciably affecting the brilliancy of the illuminant. Good. white discharges can also be obtained by using a discharge paste containing a white pigment, for which purpose titanium dioxide is particularly suitable. On the other hand satisfactory discharges are not obtainable on fabrics dyed in full shades with anthraquinone derivatives, for example fabrics containing 0.25% of 'dyestufi based on the weight of the goods.

As illuminant in the production of coloured discharges there can be used any dyestufi resistant to the discharging agent and especially suitable for this purpose is a vat dyestufl. 1

For the ground shades the best results are obtained with 1:4-diaminoanthraquinones and l-amino-4qhydroxy-anthraquinones in which one of the benzene nuclei is free from auxochromic substituents, especially amino and hydroxy groups, for example l:4-di'methylaminoanthra-. quinone or '1-amino-4-cyclohexylaminoanthraquinone-2-carboxyamide. Anthraquinone derivatives of the type of. 1:4ediethanolamino-5-= hydroxyanthraquinone and 1:4-diethanolamino= 5:8-dihydroxyanthraquinoneare not usually so satisfactory, since the colour of the reduced dyestud left .in the discharge portions may be more obtrusive. In contradistlnction to anthraquinone vat colours which on reduction give the true leuc'o or meso dihydro compounds which may be reoxidised to the original shades, the anthraquinone dyestuffs having direct ailinlty for cellulose acetate give the more stable 2:3-dlhydro-compounds, probably accompanied by scission of the amino group. They do not therefore reoxidise to the original shade.

The invention is of particular importance in connection with the production of discharge none dyestuffs or to materials dyed in a coinpound shade, part of which is due to an anthraguinone dyestuil and part to a truly dischargeable dyestuff, e. g. a dischargeable azo dye or a dischargeable nitrodiarylamine dye or other dischargeable dyes having nitro groups asthe sole is of a high order,

chromophores. For example, valuable discharges may be obtained according to the invention on materials dyed in pale green shades with a mixture of a blue anthraquinone dyestufi and a yellow dischargeable dyestufi of the above-mentioned type. As it is the blue constituent which usually gives trouble in this work when using a truly dischargeable blue dyestufl, it is found that discharges obtained upon materials dyed in pale green shades in this way are superior to those in which the dyestufi mixture consists of a truly dischargeable blue and a truly dischargeable yellow dyestuif.

The invention is illustrated by the following examples:

Example 1 Cellulose acetate fabric is dyed in a pale blue shade with either 0.025% of 1:4-di-(methylamino) -anthraquinone or 0.025% of l-amino-l-cyclohexylaminoanthraquinone 2 carboxyamide, based on the weight of the fabric, and then printed, using the following printing colours:

The dyestufi used as illuminant may be any one of the following:

Yellow:

20 parts Indanthrene Yellow GOK (Schultz, Supplement 2, page 201). Pale Blue:

2.2 parts Ciba Blue 2 Green:

(Colour Index No.

16 parts Paradone Yellow GC (an anthraquinone vat dyestufl).

4 parts Caledon Jade Green XS (Colour Index No. 1101 I. C. I. Shade Card Caledon and Durindone Dyestuffs" 1937).

Red:

13.3 parts Durindone Scarlet YS (Schultz,

Supplement 2, No. 1356).

6.7 parts Hydron Pink FF (Colour Index,

page 355).

Pink:

1.1 parts Durindone Scarlet YS.

0.55 part Hydron Pink FF.

After printing the pieces are dried, steamed and oxidised by hanging for 48 hours, washed off and soaped. The iastness of the ground shade both to light and to acid fading, and the pigment white also is of a satisfactorily high order of fastness to washing.

Example 2 Cellulose acetate material is dyed in pale green shades, using a mixture of either of the two anthraquinone dyestuffs mentioned in Example 1 and as dischargeable yellow dyestuff 2:4-dinitrodiphenylamine; 4:4 diamino 3:3 dinitrodiphenylmethane or the azo dyestufi from diazotised p-aminoacetanilide and p-cresol.

The materials are printed and after-treated as described in Example 1. The ground shade shows no appreciable modification.

Having described our invention, what we desire to secure by Letters Patent is:

1. Process for the production of patterned textile materials of an organic derivative of cellulose, which comprises locally discharging the ground color of such materials colored in pale ground shades with an amino anthraquinone dye having direct aflinity therefor, by locally applying to the materials a composition containing a sulphoxylate discharging agent.

2. Process for the production of patterned textile materials of an organic derivative of cellulose, which comprises locally discharging the ground color of such materials colored in pale ground shades with a blue amino-anthraquinone dye having direct aifinity therefor, by locally applying to the materials a composition containing a sulphoxylate discharging agent.

3. Process for the production of patterned textile materials of an organic derivative of cellulose. which comprises locally discharging the ground color of such materials colored in pale ground shades with a blue aminoanthraquinone dye having one of the benzene nuclei free from auxochromic substituents and having direct affinity for the materials, by locally applying to the materials a composition containing a sulphoxylate discharging agent.

4. Process for the production of patterned textile materials of an organic derivative of cellulose, which comprises locally discharging the ground color of such materials colored in pale ground shades with a blue aminoanthraqulnone dye having one of the benzene nuclei free from auxochromic substituents and having direct atfinity for the materials, by locally applying to the materials a composition containing a sulphoxylate discharging agent and a vat dye as illuminant.

5. Process for the production of patterned textile materials of an organic derivative of cellulose which comprises locally discharging the ground color of such materials colored in pale ground shades with a blue aminoanthraquinone dye having one of the benzene nuclei free from auxochromic substituents and having direct atfinity for the materials, by locally applying to the materials a composition containing a sulphoxylate discharging agent and a white pigment.

6. Process for the production of patterned textile materials of an organic derivative of cellulose, which comprises locally discharging the ground color of such materials colored in pale ground shades with a mixture of a blue aminoanthraquinone dye having one of the benzene nuclei free from auxochromic substituents and a truly dischargeable dye, both dyes having direct aflinity for the materials, by locally applying to the materials a composition containing a sulphoxylate discharging agent.

7. Process for the production of patterned cellulose acetate textile materials, which comprises locally discharging the ground color of such materials colored in pale ground shades with an amino anthraquinone dye having direct afflnlty therefor, by locally applying to the materials a composition containing a sulphoxylate discharging agent.

8. Process for the production of patterned cellulose acetate textile materials, which comprises locally discharging the ground color of such mazene nuclei free from auxochromic substituents and having direct amnity for the materials, by locally applying to the materials a composition containing a sulphoxylate discharging agent.

10. Process for the production of patterned cellulose acetate textile materials, which comprises locally discharging the ground, color of such materials colored in pale ground shades with a blue amino-anthraquinone dye having one of the benzene nuclei free from auxochromic substituents and having direct amnity for the materials, by locally applying to the materials a composition containing a sulphoxyiate discharging lit agent and a vat dye as illuminant.

11. Process for the production of patterned cellulose acetate textile materials, which comprises locally discharging the ground color of such materials colored in pale ground shades with a blue amino-anthraquinone dye having one of the benzene nuclei free from auxochromic sub stltuents and having direct aiilnity for the materials, by locally applying to the materials a composition containing a sulphoxylate discharging agent and a white pigment.

12. Process for the production of patterned cellulose acetate textile materials, which comprises locally discharging the ground color of such materials colored in pale ground shades with a mixture of a blue amino-a'nthraquinone dye having one of the benzene nuclei free from auxochromic substituents and a truly dischargeable dye, both dyes having direct aflinity for the materials, by locally applying to the materials a composition containing a sulphoxylate discharging agent.

HENRY CHARLES OLPIN. WILLIAM CYRIL McKNIGHT. 

